Cellulosic composition of matter containing a bromo compound



Oct. 6, 1931. s. J. CARROLL 1,826,688

CELLULOSIC COMPOSITION OF MATTER CONTAINING A BROMO COMPOUND v Filed Aug. 50, 1929 Patented ct. 3, 1931` l UNirEfsTAT-Es.-

OFFICE x y STEWART J.`CARR0'LE, or' ROCHESTER 'NEW YCRRAssiGNoR To EAsTiviAN KODAK p COMPANY, or ROCHESTER, NEWKYORE, Ap'CoRPoRATioN or NEW` YORK stances, such -.a common'solvent for both, 'With or Without other useful addition agents, so that the ire-Q` sulting product Will have'properties such lask Will make the composition highly advanta-` CELL'ULosiC CoiviPosITIoiv OEMATTER CoNT'AiNiNe A BRoMo Coivirounn Application mea Auguseso, i929. serial No. 889,451.

This-inventionrelates to compositions of matter in which cellulose derivatives,;such as cellulose acetate, cellulose nitrate or cellulose j are combined or mixed with other sub` etherA 7 as a compatible plasticizenvand geous for use in the plastic and analogous of Wrapping sheets, photographic'lilm, arti,- icial silk, varnishes or lacquers, and thelik'e.

Gne object of this invention is to produce a composition of matter Which may loe made into permanently.transparenu strong and., flexible sheets Vorffi-lmS of desired tliinnessy Which are substantially Waterproof, are unpossess the ldesired properties ot a support for sensitive photographic coatings. Another obj ectoi't' my invention is to produce a composition which is capable of easy and convenient manipulation in the plastic and analogous arts, such `as in n sheets, films, artificial silk iilaments, var-A nishe's, lacquers andthe like; and to Vproduce,

' a composition which Will not injureorjbe injured by, theisubstances or surfaces A With Which it lis, associated during manufacture,

Other and furtherY objects storage or use. Y, y Willv hereinafter become apparent to those skillediin the art to which this invention; pertains. i

l While cellulose acetates,1iitrates kand others 1 for decades it has also been knovvnthat toutilize them. in theya'rious have been 'known plastic arts it is necessary to mix therewith such plasticizing or conditioning agents as camphor, castor oil, triphenyl phosphate,v

.monochlornaphthalene or the like. Certain of these and other addition agents yare also added for the purpose of reducing the iniiammability of the product. ing agents, such as the higher alcohols and their esters,are sometimes also added. lSimilarly addition compounds of various kinds have been employed to increase flexibility,

transparency, toughness and other properties- Which Will enhance the vvalue ofthe'resulting arts, such, for instance, as themanufacture and..

the manufacture of :They each compatible With cellulose vPlastic indue product..jv Affldtion products `for the samek or similarfpurposes are also added to cellulose* acetates, nitratesand others to prepare them for use in theotherplas'tic artsy, suoli aas in the i manutacture of lacquer's, varnishes, artificial silk filaments, moulded compounds and the like.` vWhileA the plasticizers Yor other addi tion 'agent heretofore,` discovered have had their utility'fin'the art', `the increasing use to which celliilosederivatives vhave been put and p,

theincrea'sing number ci desirable properties required of the celiulose derivative forV most purposes lias'made-.the discovery of new and economical ,plasticizers or, other Vaddition' compositions containing cellulose deriva-Y Y tives, such as cellulose acetate, by .adding thereto as p-lasticizing agents'either ofthe bromo compounds para-bromobenzaldehyde or y,inethyl-ineta-brjomo-loenzoate in the presv ence of asolvent, such lfas acetone, which will Vdissolve l both fthe "cellulose derivative and plasticizer'. These plasticizers are both sol V ids vat ordinarv atmospheric temperature and havethe structural :formulae:

para bromo-benaaldeliyde .I

EL H Y inethyl-meta-broino-loenzoate;V i'

. Bl" H i rivatives I and particularlyv compatible," rWith pounds and not particularly diiiicult to produce, or obtain uponthe open market. They are related .in `that 'thev benzaldehyde .'Will l changeto a benzoate With heat andair. `:The

particularly useful properties Which A they each induce in or contribute to a cellulosic;

better understand my inventionI would state, Y um by vvay ofillustration, that for the manufacycellulose acetate in `the' per(:enta'ges*herein- `after, given. vThey are' not ,expensiveY com# ture of photographic film or other sheets my new composition of matter may be compounded as follows: 100 parts of acetone scluble cellulose acetate i. e. cellulose acetate containing from 36% to 42% acetyl radical, approximately, is dissolved with stirring at atmospheric temperature in 800 to 500 parts, preferably 400 parts, by weight, of acetone. 'l`o this solution may be added from 10 to 50 parts by weight, of para-bromo-benzaldehyde, it being found preferable tovemploy approximately 50 parts thereof. Within the limits stated, the amount of plasticizer may be decreased or increased, depending upon whether it is desired to decrease or increase, respectively, the properties which this plasticizer contributes to the finished product. rl`he amount of solvent employed may also be decreased or increased, depending upon Vwhether it is desired to have a more or less freely fiowing composition, respectively. ln the same manner and in the same proportions, methyl-metabrombenzoate may be employed as a plasticizer; for the preferred amount of this plasticizer 30 parts may be employed as well as 50 parts.

A composition of matter prepared as above described may be deposited upon any suitable film forming surface to form a film or sheet,

asis well lmown to those skilled in the art. A film yso produced has permanently brilliant transparency and exceptionally low inflammability, burning no more readily than ordinary newsprint. Such film is tough and flexible as shown by the fact that it will withstand many folds upon a modified Schopper fold-tester (commonly used for such purposes) without breaking and that even after being subjected for 37 days (in the case of either plasticizer) to air maintained at a temperature of 65 C. the film still maintains flexibility, demonstratingthat the film will withstand ordinary usage satisfactorily for many years, whereas a film formed from a mere solution of cellulose acetate in acetone vor other similar solvent is britt-le and fragile after being subjected to the same treatment for thirty days'or even a lesser time. The sum total of the above advantageous properties of a product produced from my new composition is considerably in excess of that of products produced with what have previolusly been regarded as the better plasticizers.

Other similar solvents (instead of acetone) which are compatible 4with the cellulose acetate and my new plasticizer may also occur to those skilled in this art. ln like manner this plasticizer may be compounded with other single organic esters of cellulose, such as cellulose propionate, butyrate and the like, or with mixed organic and/or inorganic esters, such as cellulose aceto-stearate, aceto-malate, or cellulose nitro-acetate, or with the cellulose ethers, a suitable solvent which will dissolve both the cellulosic derivative and the plasticizer being employed.

rlhe accompanying drawing, forming a part of this application, clearly illustrates the particular advantages of employing my novel plasticizer in the plastic arts. ln this drawing there are plotted lines or curves graphically depicting the properties of film produced from a composition containing cellulose acetate and this plasticizer. 0n the horizontal axis is indicated the various percentages of my plastici/zer that may be employed with the cellulosic derivative, this percentage being given in parts added to the cellulose derivative rather than parts of the composition; for instance, 30 parts plasticizer added to 100 parts cellulose acetate is denoted as 30% plasticizer added. On the vertical axis at (a), on the left, is indicated in percentage over the check sample the ini tial flexibility of a film which has been formed as described from my novel composition and which has been subjected to air at 50O C. for 24 hours to free it of solvent; the rate of combustion of that film is also indi cated by this same column (a) at on the right is indicated the length of time in days that the film will maintain flexibility when subjected to air kept at a temperature of 650 C. rlhere are two sets of curves. A, B and C refer to film containing para-bromobenzaldehyde and A', B and C refer to film containing methyianeta-bromo-benzoate. The (A) curves depict initial flexibility of the film, the B) curves depict the ability of the film to maintain flexibility and the (C) curves depict tlie rate of combustion of the film-all with various percentages of my novel plasticizer and all as compared to the respective properties of a lm produced from a solution of cellulose acetate in acetone and a hypothetical inert material substituted for the plasticizer as denoted by curve (D) indicating unity of 100% and 30 days for and lt will thus be noted that my novel plasticizer has the faculty of giving, to a product produced therefrom, good initial flexibility and an exceptionally low combustion rate, and that the product maintains its flexibility quite well. The combustion rate is lowered slightly more in the case of the preferred percentage of methyl-meta-bromobenzoate. The preferred percentage of either of these plasticizers which it i-s desirable to employ to contribute any particular property to the final product will be obvious from an inspection of this drawing; the best percentage to employ will' depend upon which property it is desired to feature most in the final product.

ln as much as my above described composition of matter is quite useful in the production of films and sheets it will be apparent that my new plasticizer may also be employed with advantage in the other branches ofthe plastic art. For instance, my above described l composition` of vmatter may beemployed in the manufacture of artificial silk by the dry ing spinning. It

bath it also be employed for wet Y of changing the solvent proportion or addpurpose ci cheapeningthe compositiony they f are added only to such an'cXtent as Willnot precipitate the derivative from solution.

lther usesvvitliin the vscope 'of'my inven- V tion will" also suggest Vthemselves tothose 'cizer may y Y in connection With a number of the known ing evaporation retardants such as triacetin or intermediate boiling constituents, as has been Well known in Ythe art v My novel vpla'stifalso be employed-With advantage or other high for more than a decade.

which it lacquer and varnishV formulae with may be found to be compatible. Insuch Y cases the plasticizer is: usually first put into solution with the cellulosederivative s olu-fv tion and if non-solvents are addedfor the skilled inthe art.

What I claim as my invention, and desire to be secured by Letters Patent of the United States, is: c

l. A composition of matter comprisingla cellulose derivative land one of the bromocompounds para-bromo-benzaldehyde;` and l methyl-meta-bromo-benzoate.-

2. A composition of matter comprising cellulose acetate and one of the bromo- 5 compounds para-bromosbenzaldehydeV and 'methyl-meta-bromo-benzoate f f Y j 3. A composition of matter comprising 100' y parts of cellulose acetate and approximately 30 parts of one of the bromo-compounds para Y b r o m o-benzaldehyde and methyl-metabromo-benzoate.

4. A1 composition 'of cellulose acetate and hyde.

matter comprising 5. A composition of matter comprising a Y Vcellulose derivative andmethyl-metabromobenzoate. f

6. A composition of matter comprisingy cellulose jacetate and methyl-meta-bromo-benzoate. n fx 7 A compositon of matter comprising 100 parts cellulose acetate and from 10 to 50v parts, by Weight,v of methyl-meta-bromobenzoate. l v

8. A composition of matter comprisinglOO parts of cellulose acetate and approximatelyv by Weight, of methylmeta- 30 to 50 parts, bromo-benzoate.

Signed at Rochester,- day of August, 1929. Y -A Y, v STEWART JQCARROLL.

New York,L vthis 27th spinning method. With the proper coagulatl Y' may'be desired to employ a v A composition of different viscosity or'eva-pora-` tion characteristics but this is a mere matter para-bromo-benz'alde Y 

